Fluoro-substituted phosphonic ester pesticides



United States Patent i FLUORO-SUBSTITUTED PHOSPHONIC ESTER PESTICIDES No Drawing. Application November 22, 1957 Serial No. 698,033

15 Claims. (Cl. 167-22) 'This invention relates to the production of new fluorosubstituted phosphonic esters useful as active insecticidal and miticidal toxicants.

- These new fluoro-substituted phosphonic esters conform to the general formula (RO)aI COH RII in which R is an alkyl radical, particularly an alkyl radical containing from 1 to 4 carbon atoms, R is a member of the group consisting of methyl, fluoromethyl and phenyl and R" is a fluoroalkyl radical, particularly a fluoroalkyl radical containing from 1 to 3 carbon atoms.

In the new compounds, typical examples of R are CH C H C l-L, and CH Typical examples of R are CH CHFg and C H Typical examples of R are CHFQ, CgF5, CgFq and Fluoro-substituted phosphonic esters of the general formula given above may be prepared by reacting fluorosubstituted ketones with dialkyl phosphites. This reaction may be represented by the following equation in which R, R and R have the meanings given above:

' Although the fluoro-substituted ketone and dialkyl phosphite may be charged in molar proportions of 1 mol of fiuoro-substituted ketone to about 0.8 to 1.2 mols of dialkyl phosphite, approximately equimolar proportions of the reactants are preferred.

If desired, the present reaction may be carried out in the presence of an inert organic solvent, preferably one lower boiling than the phosphonic ester produced. Suitable inert organic solvents include methylene chloride, hexane, benzene and acetone. When the reactions are completed, lower boiling solvents so used may be recovered for reuse by simple distillation at atmospheric or lower pressure.

The reaction of this invention may be conducted at any temperature up to the decomposition point of the reactants and is preferably carried out at about 20 to 100 C. Frequently, the reaction is quite vigorous during addition of the reactants, in which instance cooling is desirable to retard the reaction.

The following examples are given for the purpose of illustrating the present invention but are not intended to be limiting on the scope thereof. 'Parts are by weight.

Example 1.50 parts of phenyl pentafluoroethyl ketone were mixed with 24.5 parts of dimethyl phosphite in a reaction vessel. The reaction mixture was heated on a steam bath for 20 hours at a temperature of about 2,929,759 Patented Mar. 22, 1960 mixture. 24 parts of a white solid having a melting point of 125-l27 C. were obtained. This solid comprised the following fluoro-substituted phosphonic ester:

(cmon-i-c on 02F: The amount of phosphonic ester collected constituted 28% of theory.

Example 2.-50 parts of phenyl heptafluoropropyl ketone were mixed with 20 parts of dimethyl phosphite in a reaction vessel. The reaction mixture was heated on a steam bath for '20 hours at a temperature of about C. The reaction mixture was slurried with a solvent mixture of about 200 parts of methylene chloride and parts of hexane and was then cooled to 0 C. A solid material formed which was collected on a filter and washed with about 50 parts of the above solvent mixture. 17 parts of a solid having a melting point of 127-128 C. were obtained. This solid comprised the following fluoro-substituted phosphonic ester:

The amount of phosphonic ester collected constituted 24% of theory."

Example 3.39 parts of tetrafluoroacetone were placed in a reaction vessel provided with a stirrer. 41.4 parts of diethyl phosphite were added dropwise over a l0- minute period with stirring and cooling to maintain the reaction mixture at a temperature of 30 C. -5 C.). The reaction was continued for about 20 minutes, holding the temperature at 40-45 C. After stirring for 1 additional hour, the reaction mixture was allowed to stand for a few days. The reaction mixture was then heated to. 80 C. at 2.5 mm. mercury pressure. The residue'comprised 73.5 parts of the following phosphonic ester:

The amount of phosphonic ester collected constituted 92% of theory.

Example 4.39 parts of teterafluoroacetone were placed in a reaction vessel provided with a stirrer. 33 parts of dimethyl phosphite were added dropwise over a 10-minute period with stirring and cooling to maintain the reaction mixture at 30 C. (i5 C.).- The reaction was continued for about 20 minutes, while holding the temperature at 40-45 C. After stirring for an additional hour, the reaction mixture was allowed to stand at room temperature for a few days. The reaction mixture was then heated to 80 C. at 2.5 mm. mercury pressure. The residue comprised 69 parts of the following fiuorosubstituted phosphonic ester:-

The amount of phosphonic ester collected constituted 96% of theory.

Example 5.55 parts of dimethyl phosphite were charged into a reaction vessel provided with a gassing tube, a stirrer and a Dry Ice-cooled condenser. 66 parts of triiiuoroacetone gas were fed into the vessel through the gassing tube. The temperature of the reaction mix: ture .rose to 34 C. and was held relatively constantby the trifluoroacetonereflux, the rate of which increased answe dry mixtures or so-called wettable spray powderscontaining the phosphonic esters of the invention. These mixtures may also include inert diluents, suitable quantities of wetting or emulsifying agents and, if desired, secondary toxicants.

The aqueous spray dispersions of the invention preferably should'contain the active ingredient iri'anamount not less than $6 of a pound per 100 gallons of spray, the more usual concentrations being in the range oi i 1 of a pound per 1-00 gallons of spray.

insecticidal and'miticidal properties of the phos'phonic CH1 a (CE 0) {l esters typical of those embraced within the scope of this a invention are shown in the following table. In the table 0 (5) parts are by volume unless otherwise indicated.

. Fiuoro- Housefly Mite Pea Substituted Formulation Kill, Kill, A hid Phosphonio percent percent ill,

Ester percent 6 Compound (1)... -1 part; of a solution of phosphonic ester in acetone per 19 86. 9

' par s we er. Compound (2) 1 part of a solution of phosphonic ester in acetone I per 19 91. 6

' parts water containing 0.5% Elvanol 51-05 (commercial water-soluble synthetic polyvinyl alcohol). Compound-(4)... 1 part of a solution of phosphomc ester in acetone per 90.1

1,279 parts Sugar solution (20 pounds of sugar diluted to 100 gallons with water). Compound (3)--. 1 part of a solutionof phosphonic ester in acetone per 88.5

1,279 parts sugar solution (20 pounds of sugar diluted to 100 gallons with water). a Compound (4)--- 1 partt of a solution of-phosphonic ester in'acetone per 159 93. 9' 95A) parswaer. I, N ,7 Compound (3).-. 1 part of a solution oi'phosphonic ester in acetone per'79 93. 7

; parts Water.

4.8 grams of phosphonic ester dissolved in acetone to 100 cc. p H V I I H 5 The tests on toxicity to houseflies (Musca domestica) werejrunby spraying the indicated formulation onto glass plates and allowing them to dry. The flies were confined over the plates, and percent kill was recorded- 24 hours'aiter confinement.

= The tests on toxicity to mites The amount of phosphonic ester collected constituted 29% of theory. 1 7

As indicated above, the fiuoro-substituted phosphonic esters of this invention fi'nd' valuable application as active insecticidal and miticidal toxicants. These compounds are ordinarily applied as toxicants for combating insect and mite pests, in conjunction with a carrier which may be a solid, liquid or gaseous material. For this purpose, the phosphonic esters may be employed either in the form of aqueous sprays or dust compositions and the amount of toxicant used may vary, a sufficie'nt quantity being utilized to provide the required toxicity.

When employed in the form of a powder or dust for killing insects and mites, the above compounds or toxicants may be mixed with a substantial proportion of any suitable inert material or diluent, preferably in finely divided form, such as known grades of prepared parasiti cide carrier clays, pyrophyllite, fullers earth, bentonite, sulfur, lime, talc, whiting, diatomaceous earth, etc. Suitable dusts of this type usually contain not less than 0.25% and preferably not less than 0.5% by weight of toxicant. 7

Liquid insecticide or initic'ide sprays containing the toxicants of the invention may be prepared by first forming a solution of the compound in asuitable organic solvent, e.g., xylene, methylated naphthalenes or any highly aroitiatic petroleum-type insecticide oil, and preferably adding a small amount of wet-ting or emulsifying agent com monly employed in the art, such as diglycol ole-ate or 'pisooctyl phenyl ether or polyethylene glycol. The resulting concentrate 'slu' '"n is incorporated-with Water in quantity su'fi'ic'ient' to term an aqueous spray dispersion or emulsion having the desired active ingredient concentration.

In a preferred embodiment, aqueous spray dispersions V (Tetranychu's bi'macul'atus) were run by sprayingthe indicated formulation onto horticultural (cranberry) beau plants infested with mites. Following treatment. the plants were stored on racks in irrigated trays under greenhouse conditions. Mortality counts were made 3 days after treatment.

4 The tests on toxicity to pea aphids (Ma'crosiphum piai) were run by removing thepea aphids from infested plants, placing them on a wire screen and spraying them with the indicated formulation. Following treatment the pea aphids were confined to'untreated broad bean-plants. Record oi kill was made 3 days after treatment.

While we have described the preferred embodiments for carrying out our invention, it will be apparent that many or emulsions-stay be fdrnidby incor orating in water changes may be made without departing from the spirit of the invention. l

We claim: 1. A fluoro-substituted phosphonic ester having the following general formula: 1

R1 teen -c 01;

RII

in which R is an alkyl radical containing from 1 to 4 carbon atoms, R is a member of the group consisting of methyl, iiuoromethyl and phenyl radicals and R is a fiuoroalkyl radical containing from 1 to 3 carbon atoms.

2. A fiuoro-substi'tuted phosphonic ester having the following formula:

in which R is an alkyl radical containing from 1 to 4 carhon atoms, R is a fiuoromethyl radical and R" is a tluoroaiky-l radical containing from 1- to 3 carbonatoms. 3. A flu'oro substituted phosphonic ester having the ob lowing general formula:

II (n0')i=-r-c-on in which R is martyr radical containing from 1 to :4 carbon atoms, R isa phenyl radicaland R" is a fluoroa'lkyl radical containing fidifl 1 i5 3 Cafli'n filOiiiSJ 4. The fiuoro-substituted phosphonic ester having the following formula:

5. The fiuoro-substituted phosphonic ester having the following formula:

6. Insecticidal and miticidal compositions comprising a fluoro-substituted phosphonic ester having the following general formula:

I R, (RO)r-I COH RII wherein R is an alkyl radical containing from 1 to 4 carbon atoms, R is a member of the group consisting of methyl, fiuoromethyl and phenyl radicals and R" is a fluoroalkyl radical containing from 1 to 3 carbon atoms, together with a carrier therefor.

7. Insecticidal and miticidal compositions comprising a fluoro-substituted phosphonic ester having the following general formula:

I (R0)a1 --C0H RII wherein R is an alkyl radical containing from 1 to 4 carbon atoms, R' is a fiuoromethyl radical and R is a fluoroalkyl radical containing from 1 to 3 carbon atoms, together with a carrier therefor.

8. Insecticidal and miticidal compositions comprising a fiuoro-substituted phosphonic ester having the following general formula:

R! (RO)af COH RII wherein R is an alkyl radical containing from 1 to 4 car bon atoms, R is a phenyl radical and R" is a fluoroalkyl radical containing from 1 to 3 carbon atoms, together with a carrier therefor.

9. Insecticidal and miticidal compositions comprising the fluoro-substituted phosphonic ester having the follow ing formula: V p

0 CHF:

together with a carrier therefor.

10. Insecticidal and miticidal compositions comprising the fiuoro-substituted phosphonic ester having the following formula:

0 CHF:

(CHaOh-P-C-OH CHF:

together with a carrier therefor.

11. The process of combatting insect and mite pests which comprises exposing said pests to a fiuoro-substituted phosphonic ester having the following general formula:

wherein R is an alkyl radical containing from 1 to 4 carbon atoms, R is a member of the group consisting of methyl, fluoromethyl and phenyl radicals and R is a fluoroalkyl radical containing from 1 to 3 carbon atoms.

12. The process of combatting insect and mite pests which comprises exposing said pests to a fluoro-substituted phosphonic ester having the following formula:

wherein R is an alkyl radical containing from 1 to 4 carbon atoms, R is a fiuoromethyl radical and R" is a fluoroalkyl radical containing from 1 to 3 carbon atoms.

13. The process of combatting insect and mite pests which comprises exposing said pests to a fluoro-substituted phosphonic ester having the following general formula:

II (ROh-P-C-OH RII wherein R is an alkyl radical containing from 1 to 4 carbon atoms, R is a phenyl radical and R" is a fluoroalkyl radical containing from 1 to 3 carbon atoms.

14. The process of combatting insect and mite pests which comprises exposing said pests to the fiuoro-substituted phosphonic ester having the following formula:

0 CHF: I (C|HsO)2-PCOH CHF,

15. The process of combatting insect and mite pests which comprises exposing said pests to the fiuoro-substituted phosphonic ester having the following formula:

References Cited in the file of this patent UNITED STATES PATENTS 

6. INSECTICIDAL AND MITICIDAL COMPOSITIONS COMPRISING A FLUORO-SUBSTITUTED PHOSPHONIC ESTER AVING THE FOLLOWING GENERAL FORMULA:
 11. THE PROCESS OF COMBATTING INSECT AND MITE PETS WHICH COMPRISES EXPOSING SAID PESTS TO A FLUORO-SUBSTITUTED PHOSPHONIC ESTER HAVING THE FOLLOWING GENERAL FORMULA: 